Method of treating boilers



Patented Mar. 19, 1946 METHOD OF TREATING BOILERS Frederick C. Bersworth, Verona, N. 1., assignor to The Martin Dennis Company, Newark, N. 3., a corporation of New Jersey No Drawing. Application January 22, 1944, Serial No. 519,408

11 Claims.

This invention relates to procedure for removing scale from boilers and preventing scale formation in boilers.

In accordance with this invention it is possible to treat boilers with a composition which is not injurious to the boiler tubes or other. parts and which is capable of removing even hard, thick coatings of scale and of preventing further scale formation.

The treating composition of this invention is an aqueous solution of two principal constituents. One of these is an alkali metal salt of an alkylene polyamine tetra (or higher) acetic acid having the general formula:

MOOO-CH: CIIz-COOIVI N-alkylenc N-alkylcne -N CHi-C O OM 1. MOOC-C CHz-COOM in which M is an alkali metal and n'is zero or a positive integer and in which none of the alkylene groups contains more than four carbon atoms. The other of these constituents is an alkali metal hydroxide, or a salt thereof with a water soluble, weak acid, and has a. pH of at leastabout 8.5.

The first of these constituents, when n=zero, may be the tetra sodium (or potassium or other alkali metal salt) of ethylene diamine tetraacetic acid, or of propylene 1,2-diamine tetraacetic acid, or of propylene 1,3-diamine tetraacetic acid, or of one of the various butylene diamine tetraacetic acids. When n=1 this constituent may be the penta-alkali metal salt of diethylene triamine pentaacetic acid, or of the dipropylene triamine pentaacetic acids, etc.

The second constituent must be soluble in water and not merely colloidally dispersibl therein as is ordinary soap for example.

A third constituent which may be included to advantage, although not necessary, is any one or more of the water soluble organic polyhydroxy compounds, for example glucose, sorbitol, the hydrolysis products of corn starch, mannitol, glycerine, diethylene glycol, ethylene glycol, etc. A further example of such a polyhydroxy compound is the sugar-like polymer obtained from formaldehyde in alkaline solution. When the first component is made according to my copending application Serial No. 491,669, filed June 21, 1943, formaldehyde is used in alkaline solution and the resulting sugar-like polymer is therefore always present in the crude reaction product.

The relative proportions in the treating solution of the poly-alkali metal salt of the alkylene polyamine polyacetic acid and the other alkali preferably between 100 to 5 and 100 to 50, each respectively, depending upon the exact nature of each constituent. Best results are usually obtained with proportions between 100 to 10 and 100 to 25, each respectively. The proportions of alkylene polyamine polyacetic acid to the other alkali metal salt or hydroxide refer to preferred additions to neutral or basic solutions. If there is any acid initially present in the water to which the constituents of this invention are added, enough alkali metal salt or hydroxide must be added to bring the system to a pH of about 7, before adding said constituents in the proportions already indicated. The polyhydroxy compounds are Preferably present in about an equal molecular quantity with the alkylene polyamine polyacetic acid salt though any amount up to that point appears to be of value.

It is already known, as set forth in Munz patent 2,240,957, that compounds such as the alkali metal salts of:

0112-0 0 0H and are suitable for treating hard water to prevent the formation of precipitates. I have found, however, that such applicability is no criterion whatever of the applicability of these compounds for treating .boilers in the manner herein set forth.

These compounds described by Munz, either alone or with soaps, are entirely unsuited to the latter purpose because it is necessary that an alkali metal salt or an alkali hydroxide as described above be present with the alkylene polyamine polyacetic acid salt to obtain satisfactoryresults. It has been found that although freshly precipitated calcium salts may be dissolved by the sodium salt of ethylene diamine tetraacetic acid, this latter salt will not dissolve or loosen the hard incrustations of calcium, magnesium, and iron salts found inside boiler tubes when used alone. The addition of a relatively small proportion of alkali metal hydroxide or a water soluble alkali metal salt of a comparatively weak water soluble acid will serve to loosen and/or dissolve such scale formation as may be present. Once the scale has been all, or substantially all, removed-the tubes of the boiler may be kept free CHzCOOH metal salt or hydroxide referred to above are from scale by adding the herein described com position, but in lesser quantities. to the feed water. polyacetic acid salts having less than four -CH:COOM groups are unsuited for the present purpose, even when the alkali metal salt or hydroxide (the second constituent herein referred is resent. 'I'he theoretical considerations for the requirement that at least four -CHz--COOM groups be present are not entirely clear. Apparently the solubilizing effect is due in part, at least, to these groups, and fewer than four to a molecule is in suflicient to put the dimcultly soluble scale into solution or to loosen it.

The treating composition may be the crude reaction product produced in accordance with my copending application Serial No. 491,669, filed June 21, 1943. This may be produced by reacting an alkylene polyamine of the formula:

in which n iszero or a positive integer, and in which none of the alkylene groups contains more than four carbon atoms, with an alkali-metal cyanide and formaldehyde with sufficient sodium hydroxide to bring the pH to at least about 9. The reaction is carried out at a temperature of about 60-80" C. under sumoiently reduced pressure to cause the mixture to boil at that temperature. (Constant stirring together with the boiling'serves to remove ammonia as fast as it is formed.) It is essential in order to obtain proper yields that the free cyanide present in the reaction mixture at any one time be not more than one-quarter the amount necessary to react completely with the amine, and that the amount of free formaldehyde present in the reaction mixture at any one time be about five per cent less than the sodium cyanide present. When the reaction is substantially completed the temperature may be raised and a slight excess of formaldehyde added to react with any'unreacted cyanide.

This crude reaction product ordinarily contains enough excess alkali metal hydroxide as well as p'olyhydroxy compounds (which are produced as aside reaction by thepolymerization of formaldehyde in the presence of an alkali) to be suitable for use without modification in carrying out the procedure of this invention. If insufllcient amounts of any constituent are present, the reaction product may' .be fortified with respect to these constituents until the desired amount of each is present. It is not necessary, however, in carryin out the present invention to employ this c'rude reaction product or to prepare the alkylene polyamine polyacetic acid salts in accordance with the said copending application.

When treatment of a boiler is contemplated by the method of this invention, several factors must be first ascertained. In regard to the boiler the factors are in particular the severity of the seal- Furthermore, any of these polyamine I s am loosened at one time. The capacity and daily consumption of the boiler must be known so that the proper concentration of products may be employed. Where the degree of hardness of the water to which the compounds of this invention are being added is considerable, the amount of the alkali metal salt of an alkylene polyamine polyacetic acid must be increased by that amount necessary to keep the calcium and magnesium salts in that water in solution. (It has been found that one mol ofthe sodium salt or threequarters mol of the potassium salt of this alkylene polyamine polyacetic acid compound is suflicient to keep in solution one mol of the calcium or magnesium salts.) If the feed water is acidic, sufilcient alkali must be added to neutralize it before the usual amount of alkali is added.

The following procedure is recommended for cleaning boilers which are too badly encrusted with scale to be operated:

The boiler is filled with a solution of approximately 0.1 to 2 per cent by weight of a compound represented by the formula: Mooc-cm Nalkylene(Nalkylene )N\ Moos-ch, Hr-COOM CHr-COOM in which M is an alkali metal and n is zero or CHs-COOM a. positive integer and in which none of the allwlto 50 parts and preferably 10 to 25 parts of an alkali metal hydroxide or a water soluble alkali metal salt of a. water-soluble, weak acid, said hydroxide or salt having a pH greater than 8.5. A number of mole of a polyhydroxy compound may be added up to the number of mols of alkyl ene polyamine polyacetic acid salt. The solution should be heated to simmering for a suitable length of time, for example about a week for a badly scaled boiler. The fire is kept low enough to prevent burning of deposited sludge, but hot enough to permit some turbulence due to convection. After this period the solution and loose material is dumped and the procedure repeated. (In a very badly scaled boiler it may be necessary to repeat the operation more than twice before the boiler scale has been sufliciently removed to permit safe use of the boiler.)

Among the alkali metal salts of alkylene polyamine tetra (or higher) acetic acids which have been found satisfactory in the foregoing pro acid, propylene 1,3-diamine tetraacetic acid, 1,4-

ing, the type of boiler, the capacity, and the daily In regard to the feed butylene diamine tetraacetic acid, dipropylene LZ-triamine and 1,3-triamine pentaacetic acid, and diethylene triamine pentaacetic acid. The concentrations of these salts varied between about 0.1 and about 2 per cent, depending upon conditions of operation and of the boiler. Among the polyhydroxy compounds found to be suitable are glucose, sorbitol, glycerin, mannitol, ethylene glycol, diethylene glycol and soluble hydrolysis products of starch. These were added in equimolecular amounts or less. As the alkali metal hydroxide or salt the following are foundto be satisfactory: sodium hydroxide, sodium carbonate, sodium phosphate (Na3PO4), sodium borate. and potassium oxalate. Mixtures of the foregoing compounds in the proportions already set one per cent solution in water of the crude reaction product made as described above and in my copending application Serial No. 491,669 which, in this case, had approximately the following composition:

, Per cent Tetra-sodium salt of ethylene diamine tetraacetic acid 60 Tri-glycine sodium salt Polymeric materials 5 Sugar-like products (polyhydroxy compounds) 20 Unidentified materials (polymerized peptidelike amino acids) plus an excess of free NaOI-l amounting to A to mol per mol of the said tetra sodium salt of ethylene diamine tetraacetic acid.

Further cleaning of scale may be accomplished while the boiler is in operation. The amount of boiler feed water used is first measured, and the degree of hardness of the water as well as the substances causing the hardness is found by analysis. Sufiicient of the alkali metal hydroxide or salt is added if the water is acid to bring it to a pH of about '7, and in addition the same materials in the same quantities as outlined above for cleaning a non-operating boiler are added to the feed water. The calculated daily amount to be so added may conveniently be divided into three parts and added three times a day. Care must be taken to blow down the boiler properly at intervals or the" sludge which is removed will be collected in restricted areas and cake to a dense solid which is impossible to remove by further treatment.

It is to be further noted that as the pressure, and therefore the temperature, of the boiler is increased, it is preferable to approach the upper limit of the amount of the alkali metal salt or hydroxide specified. Apparently under the extreme conditions existing in a boiler, hydrolysis of the polyamine polyacetic acid salt tends to take place, but is repressed by the addition of alkali.

It is evident that for successful employment of this invention care is required on the part of the engineer in charge. By proper application of the principles laid down, boilers with a wide variety of characteristics and with widely diiferent scale compositions may be treated successfully.

I claim: 1. The method for treating a boiler to remove and prevent scale which comprises introducing into the feed-water of the boiler a composition containing as its essential constituents a polyalkali metal salt of an alkylene polyamine polyacetic acid of the general formula mooc-cm N-alkylenc I\IOOCC2 wherein M is an alkali metal, n is zero or a positive integer and the alkylene groups contain not more than four carbon atoms each, and 5 to 50 per cent as much by weight of a water-soluble alkaline-reacting compound having a pH of at least about 8.5 and selected from the group consisting of alkali metal hydroxides and salts of alkali metal hydroxides with relatively weak water-soluble acids, the former constituent being present in an amount not more than about two per cent of the water, by weight and maintaining the contents of said boiler at a temperature of about the boiling point.

2. The method according to claim 1 wherein the composition includes a water-soluble polyhydroxy compound in a molal quantity not greater than that of the polyalkali metal salt of the alkylene polyamine polyacetic acid.

3. Method for treating a boiler to remove scale which comprises substantially filling the boiler with an aqueous solution containing as its essential constituents a polyalkali metal salt of an alkylene polyamine -polyacetic acid of the general formula wherein M is an alkali metal, n is zero or a positive integer and the alkylene groups contain not more than four carbon atoms each, and 5 to 50 per cent as much by weight of a water-soluble alkaline-reacting compound having a pH of at least about 8.5 and selected from the group consisting of alkali metal hydroxides and salts of alkali metal hydroxides with relatively weak water-soluble acids, the former constituent being present in an amount not more than about two per cent of the water, by weight, and heating said boiler to raise the contents thereof to about boiling temperature to cause circulation of the composition by means of convection currents, but

Ulla-COOM insufficiently to cause burning of deposited wherein M is an alkali metal, n is zero or a positive integer and the alkylene groups contain not more than four carbon atoms each, free sodium hydroxide, and polyhydroxy compounds, said composition being the crude reaction product obtained by reacting an alkylene polyamine of the formula CH2COOM in which n is zero or a positive integer, and in which none of the alkylene groups contains more than four carbon atoms, with an alkali-metal cyanide and formaldehyde with sufilcient sodium hydroxide to bring the pH to at least about 9, the reaction being carried out at a temperature of about 60-80 C. under suficie'ntly reduced pressure to cause the mixture to boil at that temperature, the free cyanide present in the reaction mixture at any one time being not more than ,4; the amount necessary to react completely with the amine, and the amount of free formaldehyde present in the reaction mixture at any one time being about 5 per cent less than the cyanide present except when the reaction is substantially completed, said salt of said alkylene polyamine polyacetic acid being present in an amount between about 0.1 and about 2 per cent .by weight of the water present, and maintaining the Water solution of said composition in the boiler at about the temperature of boiling.

5. The method for treating a boiler to remove and prevent scale which comprises introducin "Moos-cu;

into said boiler an aqueous composition containing as its essential constituents a polyalkali metal salt or an alkylene polyamine polyacetic acid of the general formula OHr-OOOM aikylene N--a1kylene )N\ Br-COOM OHr-GOOM metal hydroxides with relatively weak watersoluble acids, the former constituent being present in an amount between about 0.1 and about 2 per .cent' of the water, by weight and maintaining the contents of said boiler at a temperature of about the boiling 'point.

6. The method in accordance with claim 5 in which the polyalkali metal salt of an alkylene polyamine Dolyacetic acid is the tetra sodium salt or ethylene diamine tetraacetic acid, and

said alkaline-reacting compound is sodium hydroxide.

"I. l'he method in accordance with claim 5 in l which the polyalkaii metal salt of an alkylene polyamine polyacetic acid is the penta sodium salt or diethylene triamine pentaacetic acid.

8. The method in accordance with claim 5 in which said alkaline-reacting compound is sodium carbonate.

9. The method in accordance with claim 5 in which the polyalkali metal salt of an alkylene polyamine polyacetic acid is the tetra sodium salt of ethylene diamine tetraacetic acid.

10. The method in accordance with claim 5 in which the amount of said water-soluble alkalinereactinx compound is between 10 and 25 per cent by weight oi said aikylene polyamine polyacetic acid salt.

11. The method in accordance with claim 5 in which a polyhydroxy compound is present in an amount not more than about mol for mol with said alkylene polyamine polyacetic acid salt.v

v FREDERICK C. BERSWORTH. 

